03 - SUMMARY OF CREL MAIN ACTIVITIES

MRE RESEARCH ACTIVITIES In general, research activities in CREL related to the MRE Project continued on various reactor types and topics related to multiphase reaction engineering in en

SUMMARY OF CREL MAIN ACTIVITIES

CREL research activities, achievements and funding during the period from July 1, 2007 through June 30, 2008, are briefly summarized below

Results of contract research work for individual companies are not reported here

MRE RESEARCH ACTIVITIES

In general, research activities in CREL related to the MRE Project continued on various reactor types and topics related to multiphase reaction engineering in energy, chemicals and environmental processes (e.g., clean and alternative fuels, energy/bioenergy, chemical, benign processes, environmentally beneficial catalytic processes, preparation of new materials, etc.)

I Multiphase reactors and processes: Experimental and modeling

The following types of multiphase reactors have been studied for the processes mentioned above:

Bubble and slurry bubble

Fluidized beds Stirred reactors

Circulating fluidized beds Processes in mini and micro

reactors Spouted beds Aerosol / particulate reactors

Trickle beds Bioreactors and bioprocesses

Structures beds

The broad spectrum of CREL research activities over the years on chemicals, energy and environmental processes is schematically presented in Figure 3 The underlying theme of all our research is the improved understanding and quantification of transport-kinetic interactions in multiphase reaction systems using experimentation, modeling, and CFD We are convinced that this knowledge will lead to safer, faster, more energy efficient and economical reactor selection, scale-up and design, environmental benign processes, and improved reactor control In this annual report we summarize and highlight the research activities conducted during 2007/2008

In addition, CREL is a core partner in the National Science Foundation (NSF) Engineering Research Center (ERC) for Environmentally Beneficial Catalysis Center (CEBC)

As mentioned earlier, the following are the general key areas which represent the pool for MRE research projects These topics are investigated, as needed, in close interaction and collaboration with universities, national laboratories, and companies around the world

i) Quantification of flow fields, in gas-liquid, liquid-solid, gas-solid, gas-liquid-solid systems in various reactor types via our unique radioactive particle tracking (RPT) and gamma ray computed tomography (CT) for measurement of instantaneous velocities, turbulence and backmixing parameters, time averaged circulation patterns voidage (holdup) distribution and other parameters These data are not available by other means and can be used for scale up, design and model validation This includes further development of our novel experimental techniques (RPT-CT) and other tools (optical probes, gas and liquid tracer techniques, heat transfer probes, mass transfer techniques, pressure fluctuation and pressure drop via differential pressure transducers, CCD camera, etc.) for measurement of flow, mixing, density profiles and transport in multiphase systems No other laboratory in the world has this RPT-CT combination that provides the capabilities for studying systems with large volume fraction of the dispersed phase i.e systems that we call opaque Recently, progress has been made under DOE funding for anaerobic digester (Professor M Al-Dahhan) to advance (Vesvikar, 2006) CARPT technique from single particle tracking to multiple radioactive particle tracking (MRPT) and CT from single γ-ray source to dual γ-ray source (DSCT) (Varma, 2008) where the density distribution of three moving phases can be measured simultaneously ii) Quantification of the reaction rate and kinetics, and evaluation and characterization of the existing, new or novel catalysts that are either in use in the existing processes and technologies or are developed for new and/or improved processes and technologies iii) Quantification of the impact of integrating the transport (hydrodynamics/momentum, mass and heat) and kinetics (chemistry/biology/electrochemistry) on the processes performance (i.e., conversion, selectivity, efficiency, safety, pollution generation, energy efficiency, etc.) Minireactors facilities made from Hastalloy C and titanium for oxidation, aklylation and other reaction processes equipped with IR probe (300 ml and 25

ml autoclave stirred reactors, 5 ml and 50 ml packed beds) have been developed and implemented

iv) Development of advanced models for various multiphase reactor types (e.g., bubble and slurry columns, trickle beds, packed beds, stirred tanks, risers, fluidized beds, etc.) that can be coupled with client’s proprietary kinetics for improved design, scale up, operation

or troubleshooting of commercial and pilot plant reactors This includes using first principles in the development of hydrodynamic and reactor models, integrating transport, hydrodynamics and kinetics and verifying such models with carefully planned experiments

v) Validation of CFD codes by RPT-CT and other techniques in various multiphase reactor types

vi) Development of environmentally benign process technologies (e.g clean alternative/renewable fuels and chemicals, hydrocarbon oxidation, solid acid alkylations, hydrogenations, hydroformulation and others)

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vii) Development of new concepts and reactor technology for biomass conversion to fuels and chemicals, bioprocessing, wastes treatment, carbon dioxide capture, etc

viii) Providing access to our new process concepts and ideas, facilities and expertise for potential joint projects

ix) Inventing and investigating novel reactor types for application to energy, environmental, chemical, fuel, biochemical and material processes

Over the Years on Energy, Chemicals and Environmental Processes

II PREPARATION OF NEW MATERIALS

In preparation of new materials we focus on the problems that could profit the most from implementation of reaction engineering principles in handling transport-kinetic interactions Our goal is the implementation of reaction engineering in such processes in order to speed up scale-up and technology transfer to manufacturing Our past experiences include work with:

• semiconductor silicon

• high performance composites

• microcapsules and biomaterials

Recently, CREL (Professors P.A Ramachandran and M.P Dudukovic)

is working with MEMC (Dr M Kulkarni) to advance the fluidized bed

technology for the growth of silicon particles Past accomplishments include a model for manufacture of carbon fibers, in collaboration with our Materials Research Laboratory (MRL), and development of a new encapsulating material for time release systems with the model describing such release (in collaboration with our Biological Transport Laboratory (BTL))

• In the semiconductor silicon area CREL (M.P Dudukovic, P.A.

Ramachandran and associates) developed the first models for the

Siemens decomposer for silicon deposition by hydrogen reduction of chlorosilanes, for the Komatsu decomposer and aerosol reactor for silane pyrolysis, and for the fluidized bed for growth of silicon particles via silane pyrolysis The latest effort contributed to the commercialization of a fluidized bed for silane pyrolysis by Ethyl Corporation These fluidized beds still operate at Pasadena, Texas and are owned by MEMC This was followed up by extensive modeling of the Czochralski crystal puller which resulted in suggestions for improved model based control of the process Our work was rewarded

by 2 NASA certificates of recognition Finally, with the insight of H Erk

a novel design of an acid etcher for large silicon wafers was developed and implemented All of the above know-how is available to sponsors

• The effect of sonification on the fluid boundary layers at the flat solid surface (wafer) has been quantified and the magnitude of mass transfer intensification to and from the surface has been determined

(H Erk, M.P Dudukovic)

III.PROCESS MONITORING AND CONTROL - (G McMillan)

Our advances in understanding of multiphase systems and the implementation of reaction engineering methodology in preparation of new materials can be enhanced by coupling them with various techniques for process monitoring which are also needed for control We are making sure that CREL students get exposed to advances in artificial intelligence, expert systems and computer technology; and we provide them with the opportunities to utilize and modify these by applying them to reactor design and materials preparation

Currently, Dr G McMillan, retired Solutia Senior Fellow, is interested and can be available for working with MRE sponsors for the development

of HYSYS plant dynamic model of the reactor and control system based on existing process and control system information A brief outline of such proposed effort is enclosed in the report

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2 CREL ACHIEVEMENTS

Graduation

We are proud that four graduate students successfully completed their

degrees in CREL during the 2007/2008 academic year

W Chentiang, completed his doctoral degree on bubble dynamics and

heat transfer in slurry bubble columns He is currently working at

ConocoPhillips

D Guha, completed his doctoral degree on stirred tank reactors He is

currently working at ConocoPhillips

A Shaikh, completed his doctoral degree on slurry bubble column

hydrodynamics He is currently working at Eastman Chemicals

V Varma, completed his doctoral degree on anaerobic bioreactor and

development of dual source gamma ray computed tomography (CSCT)

He is currently working at Shell

CREL Interactions:

CREL continues to maintain close contact with our industrial sponsors, National laboratories and academia all over the world

• As part of the interaction between CREL and industrial sponsors that

we encourage, some of our students and research associates held summer jobs on companies’ premises

In the past years the following CREL students and associates held industrial summer jobs:

L Han worked during the summer 2005 and 2006 at MEMC electronics,

St Louis

A Henriques, worked during the summer 2005 and 2006 at

USDA-Eastern Research Facility in Pittsburgh

D Guha worked during 2004 at Air Products and Chemicals.

J Guo worked during 2004 at Corning.

Y Jiang worked during the summer of 1999 at DuPont Engineering

K Balakrishnan worked during the Fall of 1999 at Monsanto

Yu Pan worked closely with the scientists at Exxon Research and

Engineering on

computational fluid dynamics and during 1999/2000 he frequently visited their premises

P Gupta and P Chen participated during 1999/2000 in the radioactive

tracer

experiments on the AFDU at LaPorte, Texas

P Gupta participated during the week of April 11, 1998 in the

radioactive tracer

experiments on the AFDU at La Porte, Texas as part of a joint effort among DOE, Air

Products, Shell and Washington University

Sairam Potaraju worked during the summer (May-August 1998) at

Solutia, Houston

S Kumar, J Chen, and P Gupta spent a week in Summer 1996 at

Exxon, Florham

Park, NJ

S Degaleesan was at Exxon, New Jersey for the Summer of 1994

P Gupta joined MEMC Electronic Materials, St Peters, Missouri, for the

Summer of 1995

S Karur joined Upjohn, Michigan for the Summer of 1995

M Khadilkar joined Union Carbide, Charleston, for the Summer of

1995

B Zou joined Monsanto Enviro-Chem for the Summer and Fall of 1995

• CREL has also developed strong links with nationally and

internationally recognized groups in multiphase flow and reactors and intends to further strengthen such links with

- Dr H Van Den Akker, Kramers Laboratorium at Delft University, Holland

- Dr R Mudde, Kramers Laboratorium at Delft University, Holland

- Dr H Svendsen, Trondheim Institute of Technology of the University of

Norway, Trondheim, Norway

- Dr G Eigenberger, University of Dortmund, Germany

- Dr A Lubbert, University of Hannover, Germany

- Dr R Lange, Dresden University, Germany

- Dr B Subramaniam, University of Kansas as a part of NSF-CEBC Center

activities

- Dr H Kuipers, Twente University-Holland

- Dr F Larachi, Laval University, Canada

- Dr J Chaouki, Ecole Polytechnic, Canada

- Dr J.C Charpentier, CPE-Lyon, France

- Dr K Arcuri, Syntroleum

- Dr C Coulaloglou, ExxonMobbil

- Dr J Logsdon, Ineos Nitrile

- Dr D Depaoli, OakRidge National Laboratory

- Mr D Marshall and C Barnes, Idaho National Laboratory

- Dr S Ram, Ansys Inc (CFX code)

- Dr Kashiwa, Los Alamos National Laboratory

- Dr L.-S Fan, Ohio State University

- Dr S Subbiah, Dr Jay Sanyal and Dr A Haidari, Fluent

- Dr Tim O’Hern and Dr John Torczynski, , Sandia National Laboratories

- Dr A Laurent, Nancy, France

- Dr J Grace, University of British Columbia, Canada

- Dr V Ranade, National Chemical Laboratory, Pune, India

- Dr N Papayannakos, National Technical University of Athens, Greece

- Dr Fernandez Sevilla, University of Almeria, Spain

- Dr E Molina Grima, University of Almeria, Spain

- Dr S Antal and Dr R Lahey, Rensselaer Polytechnic Institute

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- Dr R.V Chaudhari, University of Kansas

- Dr N Nicola, University of Pretoria, South Africa

- Dr V Pareek, University of Curtin, Australia

- Dr M Cassanoli University of Bo Aires, Argentina

- Dr S Nedeltchev, National Academy of Science, Bulgaria

- Dr M Rafique, IBCAST, Pakistan Centers for Excellence in Science and

Technology

- Dr Roy, IIT, New Delhi, India

- Dr S Loyalka and Dr T Ghosh, University of Missouri, Columbia

- Dr R Gardner, North Carolina State University

Strengthening of these relationships through work on joint projects and exchange of personnel is being sought

3 CREL PRODUCTIVITY AND FUNDING

We continue to report on various productivity measures of CREL such

as degrees granted per year, number of graduate students and

postdoctoral associates involved in research, and journal publications per year

Table 1: CREL PRODUCTIVITY Recent Doctoral and Master Degrees Granted for Work in CREL (1995 - present):

R Varma, Characterization of Anaerobic Bioreactors for Bioenergy Generation Using a

Novel Tomography Technique, 2008

D Guha, Hydrodynamics and Mixing in Single Phase and Liquid-Solid Stirred Tank

Reactors, 2007

C Wu, Heat Transfer and Bubble Dynamics in a Slurry Bubble Column for Fischer-Tropsch

Alternative Fuels, 2007

L Han, Hydrodynamics and Mass Transfer in a Slurry Bubble Column Reactor, DSc, May

2007

A Shaikh, Bubble and Slurry Bubble Column Reactors for Syngas to Liquid Fuel

Conversion: Mixing, Flow Regime Transition, and Scale-Up, DSc, May 2007

M Vesvikar, Understanding the hydrodynamics and performance of anaerobic digesters,

DSc, August 2006

Shaibal Roy, Phase distribution and performance studies of gas-liquid monolith reactor,

DSc, Washington University, May 2006

Fan Mei, Mass and energy balance for a corn-to-ethanol plant, MS, May 2006

RC Ramaswamy, Steady state and dynamic reactor models for coupling exothermic and

endothermic reactions, DSc, May 2006

Prakash Kumar, Aerosol routes for synthesis of nanostructured magnetic oxides:

characterization and transport behavior, DSc, Washington University, August 2005

S Bhusarapu, Solids flow mapping in gas-solid riser, Dsc, August 2005 Jing Guo, Catalytic wet oxidation over pillared clay catalyst in packed-bed

reactors: Experiments and modeling, DSc, Spring 2005

R Hoffman, Effect of modeling on the performance of anaerobic

digesters, MS, August 2005

Huping Luo, Analyzing and modeling of airlift photobioreactors for

microalgal and cyanobacteria cultures, DSc, August 2005

Peng Chen, Fluid dynamic modeling of bubble column flows DSc,

Washington University, May 2004

Booncheng Ong, Experimental investigation of bubble column

hydrodynamics: Effect of elevated pressure and superficial gas velocity, DSc, Washington University, St Louis, MO, May 2003

Eusebio Palmisano, Wetting efficiency of complex shape catalyst in

trickle bed reactors, MS, Washington University, 2003

Novica Rados, Slurry bubble column hydrodynamics: Experimentation

and modeling, DSc, Washington University, St Louis, MO, May 2003

Puneet Gupta, Churn-turbulent bubble columns: Experiments and

modeling, DSc, Washington University, St Louis, MO, May 2002

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